Tunable voltage margin access diodes

ABSTRACT

The present invention relates generally to high current density access devices (ADs), and more particularly, to a structure and method of forming tunable voltage margin access diodes in phase change memory (PCM) blocks using layers of copper-containing mixed ionic-electronic conduction (MIEC) materials. Embodiments of the present invention may use layers MIEC material to form an access device that can supply high current-densities and operate reliably while being fabricated at temperatures that are compatible with standard BEOL processing. By varying the deposition technique and amount of MIEC material used, the voltage margin (i.e. the voltage at which the device turns on and the current is above the noise floor) of the access device may be tuned to specific operating conditions of different memory devices.

BACKGROUND

The present invention relates generally to high current density accessdevices, and more particularly, to a structure and method of formingtunable voltage margin access diodes using layers of mixedionic-electronic conduction (MIEC) materials.

In order to increase the density of memory technologies (both volatileand nonvolatile), a crosspoint design is typically preferred. In such anoptimized design, the wordlines and bitlines (hereafter referred to asmemory lines) run at minimum pitch=2F, where F refers to thelithographic minimum feature size (for example, 32 nm), and storageelements are placed between these perpendicularly oriented memory linesat their crosspoints.

Two device components are needed at the crosspoint of the memory lines:(a) a memory element and (b) a rectifying diode or access device (AD).The memory element refers to an element that is used to storedata/information. Many options exist here, including, for example, phasechange memory (PCM), MRAM, Resistive RAM (RRAM), solid electrolytememory, FeRAM, etc. The rectifying element or AD is needed because atransistor is usually not provided at every crosspoint, so a device isneeded to rectify current (i.e., exhibit nonlinearity). This ensuresthat the memory cells that lie on unselected wordlines and bitlines arenot inadvertently programmed or shorted to each other and do not leakany significant amount of current.

The quality of single-crystal silicon p-n and Schottky diodes that canbe fabricated in middle-of-line (MOL) or back end of line (BEOL) lowertemperature processes is typically very low since they have to be madein amorphous or polycrystalline silicon that has much lower mobility.This may prevent the use of p-n junctions in either single-crystalsilicon or other silicon materials as rectifiers for high-current memoryelements (especially in 3D applications).

Instead of using single-crystal silicon p-n and Schottky diodes as ADsat the crosspoint of the memory lines, solid electrolyte (SE) diodes maybe used. The advantage of this approach is the high ON/OFF ratio, as theSE can provide very high currents in the ON state (since it has ametallic filament that bridges the two electrodes) and very low OFFcurrents. However, disadvantages with this approach include: the needfor an explicit erase step to erase the filament, wherein such an erasestep can be quite slow (for example, hundreds of microseconds are neededto erase a thick filament); the low reliability/endurance of the SEelement during high current programming; and the very low OFF currentactually being near or below a noise floor current in some devices.

SUMMARY

According to an embodiment, a method of forming an access diode having atunable voltage margin is disclosed. The method may include: forming amixed ionic-electronic conduction (MIEC) layer on a substrate, the MIEClayer including one or more individual layers of MoS2; doping the MIEClayer with a conductive defect dopant; forming a first electrode on theMIEC layer; and forming a second electrode on the MIEC layer, the secondelectrode separated from the first electrode by a lateral portion of theMIEC layer.

According to another embodiment, a method of tuning a voltage margin ofan access diode is disclosed. The method may include: adjusting abandgap of the access diode by varying a number of layers of a mixedelectronic-ionic conduction (MIEC) material used to electrically connecta first electrode and a second electrode; and adjusting defect energyand effective mass of the access diode by doping the MIEC material witha conductive defect dopant.

According to another embodiment, an access diode structure having atunable voltage margin is disclosed. The structure may include: a mixedelectronic-ionic conduction (MIEC) layer on a substrate, the MIEC layerincluding one or more individual layers of MoS2; a conductive defectdopant in a lattice structure of the MIEC layer; a first electrode onthe MIEC layer; and a second electrode on the MIEC layer, the secondelectrode separated from the first electrode by a lateral portion of theMIEC layer.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

The following detailed description, given by way of example and notintended to limit the invention solely thereto, will best be appreciatedin conjunction with the accompanying drawings, in which not allstructures may be shown.

FIG. 1 is a cross section view of a structure, including a substrate,according to an embodiment of the present invention.

FIG. 2 is a cross section view illustration forming a MIEC layer on thesubstrate, according to an embodiment of the present invention.

FIG. 3 is a cross section view illustrating forming one or moreelectrodes on the MIEC layer, according to an embodiment of the presentinvention.

FIG. 4 is a graphical representation illustrating the density of states(DOS) and different bandgaps of the MIEC diode with different MIEClayers, according to embodiments of the present invention.

The drawings are not necessarily to scale. The drawings are merelyschematic representations, not intended to portray specific parametersof the invention. The drawings are intended to depict only typicalembodiments of the invention. In the drawings, like numbering representslike elements.

DETAILED DESCRIPTION

Detailed embodiments of the claimed structures and methods are disclosedherein; however, it can be understood that the disclosed embodiments aremerely illustrative of the claimed structures and methods that may beembodied in various forms. This invention may, however, be embodied inmany different forms and should not be construed as limited to theexemplary embodiments set forth herein. Rather, these exemplaryembodiments are provided so that this disclosure will be thorough andcomplete and will fully convey the scope of this invention to thoseskilled in the art.

For purposes of the description hereinafter, the terms “upper”, “lower”,“right”, “left”, “vertical”, “horizontal”, “top”, “bottom”, andderivatives thereof shall relate to the disclosed structures andmethods, as oriented in the drawing figures. It will be understood thatwhen an element such as a layer, region, or substrate is referred to asbeing “on”, “over”, “beneath”, “below”, or “under” another element, itmay be present on or below the other element or intervening elements mayalso be present. In contrast, when an element is referred to as being“directly on”, “directly over”, “directly beneath”, “directly below”, or“directly contacting” another element, there may be no interveningelements present. Furthermore, the terminology used herein is for thepurpose of describing particular embodiments only and is not intended tobe limiting of the invention. As used herein, the singular forms “a,”“an,” and “the” are intended to include the plural forms as well, unlessthe context clearly indicates otherwise.

In the interest of not obscuring the presentation of embodiments of thepresent invention, in the following detailed description, someprocessing steps or operations that are known in the art may have beencombined together for presentation and for illustration purposes and insome instances may have not been described in detail. In otherinstances, some processing steps or operations that are known in the artmay not be described at all. It should be understood that the followingdescription is rather focused on the distinctive features or elements ofvarious embodiments of the present invention.

The present invention relates generally to high current density accessdevices (ADs), and more particularly, to a structure and method offorming tunable voltage margin access diodes in phase change memory(PCM) blocks using layers of copper-containing mixed ionic-electronicconduction (MIEC) materials. A MIEC diode is a two terminal diode devicecontaining a solid electrolyte (SE) material in which both electron/holecarriers and the activated dopant ion (e.g., Frenkel-pair defects) driftin an applied electric field and contribute to the total current.MIEC-based ADs may offer the large ON/OFF ratios, a high voltage marginV_(m) (over which current<10 nA), and ultra-low leakage (<10 pA) neededto enable large arrays, as well as the high current densities needed forPCM and the fully bipolar operation needed for high-performance RRAM.

Embodiments of the present invention may use layers MIEC material toform an access device that can supply high current-densities and operatereliably while being fabricated at temperatures that are compatible withstandard BEOL processing. By varying the deposition technique and amountof MIEC material used, the voltage margin (i.e. the voltage at which thedevice turns on and the current is above the noise floor) of the accessdevice may be tuned to specific operating conditions of different memorydevices. Methods by which to fabricate MIEC-based ADs having a tunablevoltage margin are described in detail below with reference to FIGS.1-4.

Referring now to FIG. 1, a cross section view of a structure 100 isshown. The structure 100 may include a substrate 102. The substrate 102may be a bulk semiconductor substrate or a semiconductor on insulator(SOI) substrate. The substrate 102 may be made from any of several knownsemiconductor materials such as, for example, silicon, germanium,silicon-germanium alloy, carbon-doped silicon, carbon-dopedsilicon-germanium alloy, and compound (e.g. III-V and II-VI)semiconductor materials. Non-limiting examples of compound semiconductormaterials include gallium arsenide, indium arsenide, and indiumphosphide. In a preferred embodiment, the substrate 102 may be composedof silicon. The substrate 102 may be approximately, but is not limitedto, several hundred microns thick. In an embodiment, the substrate 102may have a thickness ranging from approximately 0.5 mm to approximately1.5 mm.

Referring now to FIG. 2, a cross section view illustration forming aMIEC layer 202 on the substrate 102 is shown. In an embodiment, the MIEClayer 202 may be composed of molybdenum disulfide (MoS₂). MoS₂ is asemiconductor material made of layers that are weakly coupled by van derWaals forces. A layer is made of three atomic planes that are stronglybonded to each other: two hexagonal planes of sulfur atoms separated byone hexagonal plane of molybdenum atoms, with each molybdenum atomcovalently bonded to six sulfur atoms in the adjacent planes. Whenpresent in layers, the sulfur atoms of one layer may be separated fromthe molybdenum atoms of an adjacent layer by approximately 3.46angstroms. In an embodiment, the MIEC layer 202 may be doped withinterstitial or substitutional defect atoms, such as copper (Cu) orchromium (Cr). The MIEC layer 202 may be doped with the defect atoms byconventional techniques, such as, for example, epitaxial doping,sputtering, vapor-phase epitaxy, chemical vapor deposition, diffusion,and ion implantation. In an embodiment, the defect atoms may be presentin the MIEC layer 202 at a concentration ranging from approximately 1%to approximately 8%.

By varying the thickness and number of layers of MoS₂ in the MIEC layer202, multiple parameters of the MIEC layer 202, such as bandgap (eV),defect energy (eV), voltage margin (V_(m)), and effective mass(m_(o)-hole), may be tuned based on the desired application. In anembodiment, the MIEC layer 202 may be composed of a single layer of MoS₂doped with Cu. The single layer of MoS₂ may be formed using conventionaldeposition techniques, such as, for example, mechanical and chemicalexfoliation, thin film sputtering, vapor-liquid-solid technique,molecular beam epitaxy, metal-organic chemical vapor deposition, or ionbeam deposition. The single layer of MoS₂ may be doped with Cu usingconventional deposition techniques, such as, for example, epitaxialdoping, sputtering, vapor-phase-epitaxy, CVD, diffusion, or ionimplantation. In an embodiment, the single layer of MoS₂ may have athickness of approximately 6.5 angstroms.

In another embodiment, the MIEC layer 202 may be composed of two layersof MoS₂ doped with Cu arranged in a dual layer. In an embodiment, thesulfur atoms of one layer of MoS₂ may be separated from the copper atomsof the other layer of MoS2 by a distance of approximately 3.5 angstroms.This close proximity may result in physical interactions between the twolayers of Cu doped MoS₂, resulting in the dual layer having differentphysical properties than the single layer of MoS₂, as illustrated belowin Table 1. The two layers of MoS₂ may be formed using conventionaldeposition techniques, such as, for example, mechanical and chemicalexfoliation, thin film sputtering, vapor-liquid-solid, molecular beamepitaxy, metal-organic chemical vapor deposition (MOCVD), or ion beamdeposition. The two layers of MoS₂ may be doped with Cu usingconventional doping techniques, such as, for example, epitaxial doping,sputtering, vapor-phase epitaxy, molecular beam epitaxy, CVD, MOCVD,diffusion, or ion implantation. In an embodiment, the two layers of MoS₂may have a thickness ranging from approximately 1 nm to approximately1.5 nm.

In another embodiment, the MIEC layer 202 may be composed of three ormore layers of MoS₂ (i.e., bulk MoS₂) doped with Cu. The bulk MoS₂ maybe formed using conventional deposition techniques, such as, forexample, mechanical and chemical exfoliation, thin film sputtering,vapor-liquid-solid technique, molecular beam epitaxy, MOCVD, or ballmilling. The bulk MoS₂ may be doped with Cu using conventional dopingtechniques, such as, for example, epitaxial doping, sputtering,vapor-phase epitaxy, molecular beam epitaxy, CVD, MOCVD, diffusion, orion implantation. In an embodiment, the bulk MoS₂ may have a thicknessranging from approximately 10 nm to approximately 1 μm.

In another embodiment, the MIEC layer 202 may be composed of one or moreribbons of MoS₂ doped with Cu. In an embodiment, the ribbons may beformed by cutting or shaving one or more sacrificial layers of MoS₂(typically 1-3 layers) into a strip of material having a finite narrowwidth. The cutting and/or shaving process may include conventionallithography techniques, such as, for example, electron-beam lithographyor ion-beam lithography. In another embodiment, the ribbons of MoS₂ maybe formed by the chemical unzipping of MoS₂ nanotubes. The ribbons ofMoS₂ may be doped with Cu, either before or after the cutting, shaving,or unzipped processes, using epitaxial doping, sputtering, vapor-phaseepitaxy, molecular beam epitaxy, CVD, MOCVD, diffusion, or ionimplantation. The ribbons of MoS₂ may have a thickness ranging fromapproximately 6 angstroms to approximately 20 angstroms depending onwhether the ribbon is made from a single layer MoS₂ or multiple layersMoS₂. The ribbons of MoS₂ may have a width ranging from approximately 1nm to approximately 20 nm.

Referring now to FIG. 3, a cross section view illustrating forming oneor more electrodes 302 (hereinafter “electrodes”) on the MIEC layer 202is shown. The electrodes 302 may be composed of a conductive material.In an embodiment, the electrodes may be composed of a metal, such as,for example, Cu, W, Ti, Pt, Al, or alloys thereof. The electrodes 302may be formed using a conventional deposition process, such as, forexample, atomic layer deposition (ALD), chemical vapor deposition (CVD),physical vapor deposition (PVD), molecular beam deposition (MBD), pulsedlaser deposition (PLD), liquid source misted chemical deposition(LSMCD), or plating.

In an embodiment, the one or more layers of MoS₂ in the MIEC layer 202may extend vertically from an upper surface of the substrate 102.Current may flow horizontally between the electrodes 302 and through theMIEC layer 202, forming a MIEC diode 304. In an embodiment, the MIECdiode 304 may be used as an access diode in a Phase Change Memory (PCM)block.

Because of the variable thicknesses and composition of the MIEC layer202, the voltage margin of the MIEC diode 304 may be tuned to fitspecific needs. Voltage margin is defined as the range of voltage acrossthe access device for which the current through it is always below 10nA. For instance, if the current increases above 10 nA at −|V_(b)| voltson the negative side and at +|V_(a)| volts on the positive side of acurve that plots access device current versus voltage applied to the topelectrode (with the bottom electrode grounded), then the voltage marginwould be equal to |V_(a)|±|V_(b)|.

As shown in Table 1, the voltage margin can be varied significantlydepending on the composition and thickness of the MIEC layer 202. Thefollowing data is based on an ab-initio simulation (i.e., a quantummechanical parameter-free simulation using density functional theory(DFT) where many body interactions are taken into account to solvemany-particle Schrodinger equations) of a MIEC diode 304 having variousMIEC layers 202. The ab-initio simulation allows for the estimation ofmaterial properties of electronic structures, such as band gap,effective mass, thermal properties, magnetic properties, etc., as shownbelow.

TABLE 1 Material Properties of MIEC Diodes with Different MIEC LayersMIEC Defect Voltage Effective Layer Bandgap Energy Margin Mass (MoS₂—Cu)(eV) (eV) (V_(m)) (m_(o)-hole) Single Layer 1.8 0.8 1.28 0.82 Two Layers1.4 1.15 0.84 0.85 Bulk 1.2 1.0 0.76 0.87

Referring now to FIG. 4, a graphical representation illustrating thedensity of states (DOS) and different bandgaps of the MIEC diode 304with different MIEC layers 202 is shown. The graph shows the differentDOS (i.e., the number of quantum states available per energy interval)at different energy levels of the MIEC diode 304. A high DOS at aspecific energy level means that there are many states available foroccupation. As shown in FIG. 4, the different MIEC layers 202, havingdifferent band gaps, result in different DOS at different energy levels,which can enable the tuning of the MIEC diode 304 based on desiredparameters.

The descriptions of the various embodiments of the present inventionhave been presented for purposes of illustration, but are not intendedto be exhaustive or limited to the embodiments disclosed. Manymodifications and variations will be apparent to those of ordinary skillin the art without departing from the scope and spirit of the describedembodiments. The terminology used herein was chosen to best explain theprinciples of the embodiment, the practical application or technicalimprovement over technologies found in the marketplace, or to enableothers of ordinary skill in the art to understand the embodimentsdisclosed herein.

What is claimed is:
 1. A method of forming an access diode having atunable voltage margin comprising: forming a mixed ionic-electronicconduction (MIEC) layer directly on a carbon doped silicon germaniumsubstrate, the MIEC layer comprising one or more individual layers ofMoS₂; doping the MIEC layer with interstitial or substitutional copperatoms; forming a first electrode above and in direct contact with theMIEC layer; and forming a second electrode above and in direct contactwith the MIEC layer, the second electrode separated from the firstelectrode by a lateral portion of the MIEC layer.
 2. The method of claim1, wherein forming the MIEC layer on the substrate comprises: forming asingle layer of MoS₂ on the substrate.
 3. The method of claim 1, whereinforming the MIEC layer on the substrate comprises: forming a dual layerof MoS₂ on the substrate, the dual layer of MoS₂ comprising a firstlayer of MoS₂ and a second layer of MoS₂ separated from one another byapproximately 3.5angstroms.
 4. The method of claim 1, wherein formingthe MIEC layer on the substrate comprises: forming a bulk layer of MoS₂on the substrate, the bulk layer of MoS₂ comprising three or more layersof MoS₂.
 5. The method of claim 1, wherein forming the MIEC layer on thesubstrate comprises: depositing one or more ribbons of MoS₂ on thesubstrate, the one or more ribbons of MoS₂ comprising a strip ofmaterial having a finite narrow width ranging from approximately 1 nm toapproximately 20 nm.
 6. The method of claim 5, wherein depositing theone or more ribbons of MoS₂ on the substrate comprises: cutting orshaving one or more sacrificial layers of MoS₂ into strips.
 7. Themethod of claim 5, wherein depositing the one or more ribbons of MoS₂ onthe substrate comprises: chemically unzipping one or more MoS₂nanotubes.
 8. A method of tuning a voltage margin of an access diodeduring fabrication comprising: adjusting a bandgap of the access diodeby varying a number of layers of a mixed electronic-ionic conduction(MIEC) material used to electrically connect a first electrode and asecond electrode, wherein the MIEC material are above and in directcontact with a carbon doped silicon germanium substrate, and wherein thefirst electrode and the second electrode are above and in direct contactwith MIEC material; and adjusting defect energy and effective mass ofthe access diode by doping the MIEC material with a conductive defectdopant, wherein doping the MIEC material with the conductive defectdopant comprises: interstitial or substitutional doping a latticestructure of the MIEC material with copper.
 9. The method of claim 8,wherein varying the number of layers of MIEC material comprises: forminga single layer of MoS₂ on a substrate.
 10. The method of claim 8,wherein varying the number of layers of MIEC material comprises: forminga dual layer of MoS₂ on a substrate, the dual layer of MoS₂ comprising afirst layer of MoS₂ and a second layer of MoS₂ separated from oneanother by approximately 3.5angstroms.
 11. The method of claim 8,wherein varying the number of layers of MIEC material comprises: forminga bulk layer of MoS₂ on a substrate, the bulk layer of MoS₂ comprisingthree or more layers of MoS₂.
 12. The method of claim 8, wherein varyingthe number of layers of MIEC material comprises: depositing one or moreribbons of MoS₂ on a substrate, the one or more ribbons ofMoS₂comprising a strip of material having a finite narrow width rangingfrom approximately 1 nm to approximately 20 nm.
 13. An access diodestructure having a tunable voltage margin comprising: a mixedelectronic-ionic conduction (MIEC) layer above and in direct contactwith a carbon doped silicon germanium substrate, the MIEC layercomprising one or more individual layers of MoS₂; a conductive defectdopant in a lattice structure of the MIEC layer, the conductive defectdopant comprising copper; a first electrode above and in direct contactwith the MIEC layer; and a second electrode above and in direct contactwith the MIEC layer, the second electrode separated from the firstelectrode by a lateral portion of the MIEC layer.
 14. The access diodestructure of claim 13, wherein the MIEC layer comprises: a single layerof MoS₂ on the substrate.
 15. The access diode structure of claim 13,wherein the MIEC layer comprises: a dual layer of MoS₂ on a substrate,the dual layer of MoS₂ comprising a first layer of MoS₂ and a secondlayer of MoS₂ separated from one another by approximately 3.5 angstroms.16. The access diode structure of claim 13, wherein the MIEC layercomprises: a bulk layer of MoS₂ on the substrate, the bulk layer of MoS₂comprising three or more layers of MoS₂.
 17. The access diode structureof claim 13, wherein the MIEC layer comprises: one or more ribbons ofMoS₂ on a substrate, the one or more ribbons of MoS₂comprising a stripof material having a finite narrow width ranging from approximately 1 nmto approximately 20 nm.